Copolymer resin, preparation thereof, and photoresist using the same

ABSTRACT

The present invention relates to a copolymer resin for a photoresist used in far ultraviolet ray such as KrF or ArF, process for preparation thereof, and photoresist comprising the same resin. The copolymer resin according to the present invention is easily prepared by conventional radical polymerization due to the introduction of mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate unit to a structure of norbornene-maleic anhydride copolymer for photoresist. The resin has high transparency at 193 nm wavelength, provides increased etching resistance and settles the problem of offensive odor occurred in the course of copolymer resin synthesis. Further, as the resin composition can be easily controlled due to the molecular structure, the resin can be manufactured in a large scale.

BACKGROUND OF THE INVENTION

[0001] The present invention generally relates to a copolymer resin for a photoresist used in the manufacture of electronic devices. The photoresist can be used with an ultraviolet ray such as KrF or ArF. More particularly, the present invention relates to processes for preparation of the photoresist, processes using the photoresist, and the photoresist itself. In an exemplary embodiment, the invention relates to a photoresist resin, wherein a mono-methyl cis-5-norbornene-endo-2,3-dicarboxylate unit has been introduced to a norbornene-maleic anhydride copolymeric structure for a photoresist, usable in lithography process using a KrF (248 nm) or ArF (193) light source which could be applied in 1G or 4G DRAM devices, and others; a process for preparation thereof; and a photoresist containing the same resin.

[0002] Various types of photoresists have been used or proposed. These photoresists often have a variety of characteristics or properties such as etching resistance, adhesiveness, and others. In general, etching resistance, adhesiveness with low light absorption at 193 nm wavelength are desirable for a copolymer resin for ArF. The copolymer resin also should be developable by using 2.38 wt % aqueous tetramethylammonium hydroxide (TMAH) solution. It is difficult to synthesize a copolymer resin, however, satisfying one or more of these properties. Many researches have focused on studies on norbolac type resin as a resin to increase transparency at 193 nm wavelength and increase etching resistance. As an example, “Bell Labs” tried to introduce alicyclic unit to the backbone chain in order to enhance etching resistance. The copolymer resin in which the backbone chain has norboran, acrylate and maleic anhydride substituent, is, for example, represented by chemical formula I:

[0003] The copolymer resin of formula I, in which maleic anhydride portion (A portion) used for polymerizing alicyclic olefin group, however, is the only material to be polymerized with norbornene, the alicyclic unit, without absorbing ArF light having 193 nm wavelength. Accordingly, it generally cannot be used as a resin for ArF, because it is quite soluble in 2.38% aqueous TMAH solution. The solubility occurs even without exposure to create a ‘top loss’ phenomenon (the top of pattern being formed in round shape) which is generally seen in conventional photoresist patterning.

[0004] Thus, in order to prevent such phenomenon, a y-portion having tert-butyl substituent should be increased. A relative decrease of z-portion, which enhances sensitivity and adhesiveness with substrate, causes disadvantages in that the photoresist is removed from the wafer in conventional patterning so that the pattern cannot be formed effectively. Other resist products have been proposed, but these resist products can have numerous limitations such as difficulty in manufacturing, offensive odors, and the like.

[0005] From the above, it is seen that a photoresist having better adhesiveness and improved resolution is desired.

SUMMARY OF THE INVENTION

[0006] According to the present invention, the present inventors developed a maleic anhydride type copolymer resin comprising 5-norbonen-2-carboxylic acid monomer represented by chemical formula II as a main constituent, and filed a patent application (Korean Patent Application No. 97-26807 filed on Jun. 21, 1997), as an attempt to solve limitations of conventional photoresist products.

[0007] Though photoresist using the maleic anhydride type copolymer resin suggested by the above application is a polymer resin with high adhesiveness, sensitivity and excellent resolution, there is a problem in practical manufacturing, because one of the main constituents, 5-norbonen-2-carboxylic acid may generate very offensive odor during the synthetic process. Thus, the present inventors have developed a novel photoresist having excellent resolution without causing the problem of offensive odor.

[0008] In a specific embodiment, the present invention provides a technique for limiting the offensive odor caused by conventional resist products. More particularly, the present invention provides a method of introducing mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate unit instead of 5-norbonen-2-carboxylic acid in the norbornene-maleic anhydride copolymer structure. The present method resolves, in part, any problem of emitting an offensive odor. In a preferred embodiment, the present method provides a resulting resist without substantially deteriorating resist sensitivity. The present photoresist also has characteristics such as excellent adhesiveness and resolution (0.13 μm). The present resist can be obtained with easiness of control of constituent composition during the synthesis of photoresist resin to make the mass production possible.

[0009] Numerous advantages or benefits are achieved by way of the present invention over conventional techniques. In a specific embodiment, the present invention provides a copolymer resin comprising mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate unit. In an alternative embodiment, the present invention provides a process for preparing the copolymer resin comprising mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate unit. In still a further embodiment, the present invention provides a photoresist comprising the above norbornene-maleic anhydride copolymer resin, organic solvent, and an inorganic acid generator. Still further, the present invention provides a semiconductor element manufactured by using the photoresist comprising the above copolymer resin. These and other benefits are described throughout the specification and more particularly below.

DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention relates to a copolymer resin for photoresist comprising mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate unit, which is represented by following chemical formula III:

[0011] where, R represents tert-butyl, tetrahydropyranyl, tetrahydrofuranyl or ethoxyethyl group, and the ratio x:y:z is (0.1-99%):(0.1-99%):(0.1-99%).

[0012] The copolymer resins according to an embodiment of the present invention preferably include norbornene-maleic anhydride copolymer resins represented by chemical formula IV to VII.

[0013] In the formulas, R, x, y and z is defined as above.

[0014] The copolymer resin of the present invention, represented by formula III can be prepared by polymerizing the norbornene derivative of formula VIII, 2-hydroxyethyl-5-norbonen-2-carboxylate of formula IX, maleic anhydride of formula X and mono-methyl-cis-5-norbonen-endo-2,3-dicarboxylate of formula XI in the presence of radical initiator.

[0015] In the above formulas, R represents tert-butyl, 2-tetrahydropyranyl, 2-tetrahydrofuranyl or ethoxyethyl or like groups.

[0016] In the preparation of the copolymer resin according to the present invention, norbornene derivatives of chemical formula VIII is preferably selected from a group consisting of tert-butyl 5-norbonen-2-carboxylate, 2-tetrahydropyranyl 5-norbornene-2-carboxylate, 2-tetrahydrofuranyl 5-norbonen-2-carboxylate and 2-ethoxyethyl 5-norbonen-2-carboxylate.

[0017] The copolymer resins according to the present invention can be prepared by a conventional polymerization process such as bulk polymerization or solution polymerization. As a solvent, cyclohexanone, methyl ethyl ketone, benzene, toluene, dioxane and/or dimethylformamide may be used individually, or in a mixture. Polymerization initiators usable in the present invention include benzoyl peroxide, 2,2′-azobisisobutyronitrile (AIBN), acetyl peroxide, lauryl peroxide, tert-butyl peracetate, di-tert-butyl peroxide, or the like.

[0018] In the process for preparing the copolymer resin according to the present invention, general polymerization condition including temperature and pressure of radical polymerization may be controlled dependent upon the property of the reactants, but it is preferable to carry out the polymerization reaction at a temperature between 60 and 200°C.

[0019] The copolymer resin according to the present invention can be used in the formation of a positive micro-image by preparing a photoresist solution in which the resin is mixed with an organic solvent and a conventional inorganic acid generator according to a conventional process for preparing a photoresist composition. In the process for forming photoresist pattern of semiconductor element, the amount of the copolymer resin according to the present invention depends on the organic solvent or photo acid generator used, and the condition of lithography, but conventionally it is about 10 to 30% by weight on the basis of the organic solvent used in the preparation of the photoresist.

[0020] The process for forming a photoresist pattern of a semiconductor device by using the copolymer resin according to the present invention is described in detail here-in-below:

[0021] The copolymer resin according to the present invention is dissolved in cyclohexanone at a concentration of 10 to 30% by weight. Photo acid generator (0.1-10 wt), such as triphenylsulfonium triplate, dibutylnaphthylsulfonium triplate, 2,6-dimethylphenylsulfonate, bis(arylsulfonyl)-diazomethane, oxime sulfonate or 2,1-diazonaphthoquinon-4-sulfonate, is incorporated to the photoresist resin. The mixture is then filtered through an ultra-micro filter to prepare photoresist solution. The photoresist solution is spin-coated on a silicon wafer to form a thin film, which is then soft-baked in an oven at 80-150° C. or on a hot plate for 1-5 minutes, exposed to light by using far ultraviolet exposer or an eximer laser exposer, and baked at a temperature between 100° C. and 200° C. for 10 seconds to 60 minutes. The exposed wafer is impregnated in 2.38% aqueous TMAH solution for 1 to 30 seconds to obtain a positive photoresist pattern.

[0022] A better understanding of the present invention may be obtained in light of following examples which are set forth to illustrate, but are not to be construed to limit, the present invention.

PREPARATION EXAMPLE I Synthesis of tert-butyl 5-norbonen-2-carboxylate

[0023]

[0024] In a reactor, cyclopentadiene (66 g) and tetrahydrofuran solvent (500 g) were charged, and the mixture was stirred homogeneously. To the reaction mixture, tert-butyl acrylate (128 g) was added, and the resultant mixture was stirred at a temperature between −30° C. and 60° C. for about 10 hours to carry out the reaction. When the reaction was completed, the solvent was removed by using a rotary evaporator, and the residue was distilled under reduced pressure to obtain 176 g (yield: 90%) of tert-butyl 5-norbonen-2-carboxylate represented by chemical formula VIIIa.

PREPARATION EXAMPLE II Synthesis of 2-hydroxyethyl 5-norbonen-2-carboxylate (Formula IX)

[0025] The same procedure described in Preparation Example I was repeated but 2-hydroxyethyl acrylate (116 g) was used instead of tert-butyl acrylate to give 155 g (yield: 85%) of 2-hydroxyethyl 5-norbonen-2-carboxylate represented by the above described formula IX.

PREPARATION EXAMPLE III Synthesis of 2-tetrahydropyranyl 5-norbonen-2-carboxylate

[0026]

[0027] The same procedure described in Preparation Example I was repeated but 2-tetrahydropyranyl acrylate (156 g) was used instead of tert-butyl acrylate to give 186 g (yield: 84%) of 2-tetrahydropyranyl-5-norbonen-2-carboxylate represented by formula VIIIb.

PREPARATION EXAMPLE IV Synthesis of 2-tetrahydrofuranyl 5-norbonen-2-carboxylate

[0028]

[0029] The same procedure described in Preparation Example I was repeated but 2-tetrahydrofuranyl acrylate (144 ) was used instead of tert-butyl acrylate to give 172 g (yield: 82%) of 2-tetrahydrofuranyl-5-norbonen-2-carboxylate represented by formula VIIIc.

PREPARATION EXAMPLE V Synthesis of 1-ethoxyethyl 5-norbonen-2-carboxylate

[0030]

[0031] The same procedure described in Preparation Example I was repeated but ethoxyethyl acrylate (144 g) was used instead of tert-butyl acrylate to give 174 g (yield: 83%) of l-ethoxyethyl-5-norbonen-2-carboxylate represented by formula VIIId.

PREPARATION EXAMPLE VI Synthesis of mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate (Formula XI)

[0032] In a reactor, cyclopentadiene (66 g) was charged, and tetrahydrofuran solvent (500 g) and maleic anhydride (98 g) were added thereto, and the mixture was stirred homogeneously. To the reaction mixture, pure ethanol (500 g) was added and the reaction was carried out with stirring at 50° C. for 8 hours. When the reaction was completed, the solvent was removed by using a rotary evaporator, and the residue was distilled under reduced pressure to obtain 156 g (yield: 87%) of mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate represented by chemical formula XI.

EXAMPLE I Synthesis of poly[tert-butyl 5-norbonen-2-carboxylate/2-hydroxyethyl 5-norbonen-2-carboxylate/mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate/maleic anhydride] copolymer resin (Formula IV)

[0033] In tetrahydrofuran or toluene, dissolved were maleic anhydride (1 mol), tert-butyl 5-norbonen-2-carboxylate (0.5-0.9 mol) prepared according to Preparation Example I, 2-hydroxyethyl 5-norbonen-2-carboxylate (0.05-0.8 mol) prepared according to Example II, and mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate (0.01-0.5 mol) prepared according to Preparation Example VI. Then, 2,2′-azobisisobutyronitrile (AIBN) (0.5-10 g), as a polymerization initiator, was added thereto, and the reaction was performed at a temperature between 65° C. and 70° C. under nitrogen or argon atmosphere for 4-24 hours. Crude product thus obtained was precipitated from ethyl ether or hexane, and the precipitate was dried to give the title copolymer resin (Formula IV) having molecular weight of 3,000-100,000 (yield: 63%). The copolymer resin thus prepared has high transparency to ArF light, increased etching resistance and excellent adhesiveness, and is developable by 2.38 wt % aqueous TMAH solution.

EXAMPLE II Synthesis of poly[2-tetrahydropyranyl 5-norbonen-2-carboxylate/2-hydroxyethyl 5-norbonen-2-carboxylate/mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate/maleic anhydride] copolymer resin (Formula V)

[0034] The same procedure described in Example 1 was repeated but 2-tetrahydropyranyl 5-norbonen-2-carboxylate prepared according to Preparation Example III was used instead of tert-butyl 5-norbonen-2-carboxylate, to obtain the title copolymer resin (formula V) having molecular weight of 3,000-100,000 (yield: 68%). Though the protective group of the copolymer resin thus prepared was substituted by acetal group, etching resistance of the resin was not deteriorated, and the resin had excellent sensitivity (sensitivity: 11 Nj/cm²)

EXAMPLE III Synthesis of poly[2-tetrahydrofuranyl 5-norbonen-2-carboxylate/2-hydroxyethyl 5-norbonen-2-carboxylate/mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate/maleic anhydride] Copolymer Resin (Formula VI)

[0035] The same procedure described in Example 1 was repeated but 2-tetrahydrofuranyl 5-norbonen-2-carboxylate prepared according to Preparation Example IV was used instead of tert-butyl 5-norbonen-2-carboxylate, to obtain the title copolymer resin (formula VI) having molecular weight of 4,000 -100,000 (yield: 64%). The copolymer resin thus obtained had similar properties to that of Example II.

EXAMPLE IV Synthesis of poly[1-ethoxyethyl 5-norbonen-2-carboxylate/2-hydroxyethyl 5-norbonen-2-carboxylate/mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate/maleic anhydride] copolymer resin (Formula VII)

[0036] The same procedure described in Example 1 was repeated but 1-ethoxyethyl 5-norbonen-2-carboxylate prepared according to Preparation Example V was used instead of tert-butyl 5-norbonen-2-carboxylate, to obtain the title copolymer resin (formula VII) having molecular weight of 4,000-100,000 (yield: 59%). The copolymer resin thus obtained had similar properties to that of Example I, but had better properties in view of contrast.

EXAMPLE V

[0037] The copolymer resin (Formula IV) (10 g) obtained according to Example 1 was dissolved in 3-methoxymethyl propionate (40 g, solvent), and triphenylsulfonium triplate or dibutylnaphthylsulfonium triplate (about 0.2-1 g) as an photo acid generator, was added thereto. After stirring, the mixture was filtered through a 0.10 μm filter to give a photoresist solution. Then the photoresist solution was spin-coated on a surface of a wafer to prepare thin film having the thickness of 0.4-1.2 μm, and the wafer was soft-baked in an oven of 70-150° C. or on a hot plate for 1-5 minutes. After exposing to light of 250 nm wavelength by using an exposer, it was post-baked at 90-160° C. Then, the exposed wafer was dipped in an aqueous TMAH solution having a concentration of 0.01-5% by weight as a developing solution, for 1.5 minutes to obtain ultra-micro photoresist pattern (resolution: 0.13 μm).

[0038] Example VI

[0039] The same procedure described in Example V was repeated except using the copolymer resin (formula V) prepared according to Example II as a photoresist resin, to form an ultra-micro photoresist pattern.

[0040] Example VII

[0041] The same procedure described in Example V was repeated except using the copolymer resin (formula VI) prepared according to Example III as a photoresist resin, to form an ultra-micro photoresist pattern.

[0042] Example VIII

[0043] The same procedure described in Example V was repeated except using the copolymer resin (formula VII) prepared according to Example I V as a photoresist resin, to form a photoresist pattern.

[0044] In case that a pattern is formed by using the photoresist as described above, a semiconductor element having micro-pattern of 0.13 μm can be manufactured, so that highly integrated element can be advantageously obtained.

[0045] As described above, the copolymer resin for KrF (248 nm) or ArF (193 nm) photoresist according to the present invention is easily pre pared by conventional radical polymerization due to the introduction of mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate unit to the polymer structure. The resin has high transparency at 193 nm wavelength, provides increased etching resistance and settles the problem of offensive odor occurred in the course of copolymer resin synthesis. Further, as the resin composition can be easily controlled due to the molecular structure, the resin can be manufactured in a large scale. Thus, the copolymer resin for KrF or ArF according to the present invention can be usefully employed in lithography process.

[0046] Many modifications and variations of the present invention are possible in light of the above teachings. Therefore, it is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described. 

What is claimed is:
 1. A copolymer resin having molecular weight of 3,000-100,000, which comprises mono-methyl cis-5-norbonen-endo-2,3-dicarboxylate monomer and is represented by following formula III

wherein, R represents tert-butyl, hydropyranyl, hydrofuranyl or ethoxyethyl group, and the ratio x:y:z is (0.1-99%):(0.1-99%):(0.1-99%).
 2. A copolymer resin in accordance with claim 1, which is norbornene-maleic anhydride copolymer resin represented by following formula IV:

wherein, the ratio x:y:z is (0.1-99%):(0.1-99%):(0.1-99%).
 3. A copolymer resin in accordance with claim 1, which is norbornene-maleic anhydride copolymer resin represented by following formula V:

wherein, the ratio x:y:z is (0.1 -99%):(0.1-99%):(0.1-99%).
 4. A copolymer resin in accordance with claim 1, which is norbornene-maleic anhydride copolymer resin represented by following formula VI:

wherein, the ratio x:y:z is (0.1-99%):(0.1-99%):(0.1-99%).
 5. A copolymer resin in accordance with claim 1, which is norbornene-maleic anhydride copolymer resin represented by following formula VII:

wherein, the ratio x:y:z is (0.1-99%):(0.1-99%):(0.1-99%).
 6. A process for preparing the copolymer resin of formula III defined by claim 1, which comprises the step of polymerizing, in the presence of a radical initiator, the norbornene derivative represented by formula VIII, 2-hydroxyethyl-5-norbornene-2-carboxylate represented by formula IX, maleic anhydride represented by formula X and mono-methyl-cis-5-norbonen-endo-2,3-dicarboxylate represented by formula XI:

wherein, R represents tert-butyl, 2-tetrahydropyranyl, 2-tetrahydrofuranyl or 1-ethoxyethyl.
 7. A process in accordance with claim 6, wherein the norbornene derivative is tert-butyl 5-norbonen-2-carboxylate presented by the following formula VIIIa:


8. A process in accordance with claim 6, wherein the norbornene derivative is 2-tetrahydropyranyl 5-norbonen-2-carboxylate presented by the following formual VIIIb:


9. A process in accordance with claim 6, wherein the norbornene derivative is 2-tetrahydrofuranyl 5-norbonen-2-carboxylate presented by the following formula VIIIc:


10. A process in accordance with claim 6, wherein the norbornene derivative is 1-ethoxyethyl 5-norbonen-2-carboxylate presented by the following formual VIIId:


11. A process for preparing the copolymer resin in accordance with claim 6, wherein the polymerization initiator is selected from the group consisting of benzoyl peroxide, 2,2′-azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate and di-tert-butyl peroxide.
 12. A process for preparing the copolymer resin in accordance with claim 6, wherein the polymerization is carried out in the presence of a solvent or a solvent mixture selected from the group consisting of cyclohexanone, methyl ethyl ketone, benzene, toluene, dioxane and dimethylformamide.
 13. A process for preparing the copolymer resin in accordance with claim 6, wherein the polymerization is carried out at a temperature between 60° C. and 200° C. under argon or nitrogen atmosphere.
 14. A photoresist composition comprising a norbornene-maleic anhydride copolymer resin defined by claim 1, an organic solvent and an photo acid generator.
 15. A photoresist composition in accordance with claim 14, wherein the photo acid generator is triphenylsulfonium triplate or dibutylnaphthylsulfonium triplate.
 16. A photoresist composition in accordance with claim 14, wherein the copolymer resin is contained in an amount between 10 wt % and 30 wt % on the basis of the amount of solvent.
 17. A photoresist composition in accordance with claim 14, wherein the photo acid generator is contained in an amount between 0.01 wt % and 10 wt % on the basis of the amount of the copolymer resin.
 18. A semiconductor device manufactured by using the photoresist composition of claim
 14. 